Treatment of textile fabrics with 1, 1, 3-tris-(2, 3-epoxyalkoxy) butanes



Uni-ted States Patent Ofifiee 3,24,l35 Patented Mar. 6, 1962 Union Carbine Corporation, a corporation of New York No Drawing. Fiied Dec. 27, 1960, Ser. No. 78,240 Ciaims. (Cl. 117-1394) This invention relates, in general, to a process for the treatment of cellulosic textile materials. In one aspect, this invention relates to the treatment of cellulosic and cellulosic-containing textile fabrics with l,1,3-tris-(2,3 epoxypropoxy)butane.

This application is a continuation-in-part of an application entitled The Treatment of Textile Fabrics With l,1,3-Tris-(2,3-Epoxypropoxy)Butane, Serial No. 844,- 160, filed October 5, 1959, now abandoned.

With the increased use of synthetic fibers, textile materials have been produced which can be washed, dried and worn with little or no ironing. These wash-and-wear properties of the synthetic fibers have stimulated a corresponding technological advancement in the field of the cellulosic fibers so that today shrink and crease-resistant properties can be imparted to cotton, rayon and linen fabrics by the use of appropriate chemical finishes. The most commonly used finishes are the formaldehyde reaction products of nitrogen-containing chemicals such as urea-formaldehyde, melamine-formaldehyde, dimethylol ethylene urea and the like. While the treatment of cellulosic fabrics with the aforementioned finishes imparts the desired shape-holding properties to the fabric, the use of nitrogen containing finishes is subject to several disadvantages. For example, the effectiveness of these treatments diminishes after repeated commercial launderings and such finishes tend to retain chlorine from bleaching solutions which results both in a yellowing of the fabric and a measurable loss of strength after ironing.

The more recent developments of new finishes for cellulosic and cellulosic-containing fabrics have been directed to the polyepoxides which can be applied to the fabrics in various aqueous or emulsified forms and thereafter cured within the fibers by means of an epoxy curing agent. While these new finishes are an improvement over the nitrogen-containing products, they are still subject to certain deficiencies. The use of a softener is required in many cases to overcome the harsh feel imparted to the fabric by the polyepoxide finish and additionally, the yellowing of the softener itself during the curing stage may necessitate the use of a bleach. While a few of the polyepoxides are slightly soluble in water, their solubility is such that it is not advantageous to prepare treating baths of such low concentrations since it would necessitate repeated padding to obtain the desired add-on of polyepoxide. For these reasons the polyepoxides usually require an emulsifying agent or non-aqueous solvent in order to prepare a bath of suitable concentration. This is particularly evident when polyepoxide polymers of high molecular weight are used. The use of non-aqueous solvents to circumvent the low solubility in water of the polyepoxide finishes also creates plant operating problems which detract from their other advantages.

A further disadvantage noted in the use of the polyepoxides to impart wash-and-wear properties is the inability to satisfactorily remove the finish in the event of over-treatment without injury to the fabric itself. In many instances the use of an excessive amount of the polyepoxide can impart an undesirable crispness or stiffness to the fabric. If the fabric is to have a soft feel, such as that intended for dresses, shirts and the like, the

amount of polyepoxide must be controlled rather carefully. None of the commercially available polyepoxide finishes is easily removed from the fabric in the case of over-treating without affecting the physical properties of the fabric itself.

Accordingly, one or more of the following objects will be achieved by the practice of the instant invention. It is an object of the present invention to provide a new process for the treatment of cellulosic and cellulosic-containing textile materials wherein the disadvantages previously indicated are substantially eliminated. It is also an object of the present invention to provide a process for impregnating cellulosic and cellulosic-containing textile materials with monomeric polyepoxides whereby the material is rendered both shrink and crease resistant, while imparting to the material after laundering, a soft, smooth finish without ironing. A further object of the present invention is to provide a process for treating textile fabrics which will not exhibit undesirable chlorine retention properties and which are durable to laundering. Another object is to provide a process for treating textile materials which does not require the use of emulsifying agents or non-aqueous solvents. A further object of the present invention is to provide textile treating solutions containing a novel polyepoxide which when applied to a textile fabric can be cured quickly and at temperatures lower than here tofore possible. Another object is to provide a process for treating textile materials with a polyepoxide .which can subsequently be stripped from the material in the case of overtreatment without harm to the fabric and the fabric thereafter retreated. These and other objects will readily become apparent to those skilled in the art in the light of the teachings herein set forth.

A broad aspect of this invention is directed to a process for treating cellulosic and cellulosic-containing textile materials whereby the material is rendered both shrink and crease resistant while imparting to the material after laundering a soft, smooth finish without ironing which comprises impregnating the textile material with a 1,1,3-tris-(2,3-epoxyalkoxy)butane and thereafter heating the material to cure the polyepoxide. Suitable polyepoxides include 1,1,3-tris-(2,3-epoxypropoxy)butane, 1,1,3-tris(2,3-epoxybutoxy)butane, and the like.

The preparation of the novel polyepoxides employed in the process of this invention is disclosed in a copending application entitled Epoxy Acetals, Serial No. 820, 871, filed June 17, 1959, by Benjamin Phillips and Paul S. Starcher, and assigned to the same assignee as the instant invention. These polyepoxides can be produced in relatively high yields by the reaction of one mole of crotonaldehyde with at least three moles of an unsaturated alcohol such as allyl alcohol, crotyl alcohol, and the like, followed by epoxidation of the olefinic linkages contained in the resulting acetal. Epoxidation of the unsaturated acetal can be conveniently carried out at temperatures within the range of from -25 C. to C. with a suitable epoxidizing agent such as peracetic acid, perpropionic acid, perbenzoic acid, and the like. i

The term cellulosic textile fabric as used throughout the specification and claims is intended to include cellulose or cellulose-containing fibers, Whether in the finished state or at some intermediate stage in processing; cellulose and cellulose-containing fabrics whether woven or knitted; and garments or other articles made from such fabrics. Thus, materials containing cellulose, regenerated cellulose, and mixtures of the two are intended to be within the scope of the present invention.

By applying a polyepoxide, such as l,1,3-tris-(2,3-ep oxypropoxy)butane, in the form of a stable aqueous solution, the disadvantages inherent in the past have been overcome to give a fabric which is soft, white and has a high degree of crease recovery, shrink resistance and wash-and-wear characteristics. The cellulosic textile fabrics treated by the process of this invention retain these properties well after repeated laundering and are not subjected to chlorine retention. Both whiteness and the original strength of the fabric are retained to a surprisingly high degree. Treatment by the method of this invention represents an improvement over other highly dgfable, non-chlorine retentive finishes heretofore availa e.

A further improvement over other comercially used polyepoxides is noted in the curing of l,l,3-tris-(2,3-epoxypropoxy)butane on the cellulosic material. The curing process can be conducted faster and at lower temperatures with consequently less damaging effect on the color and the fabric itself. Additionally, a well-recognized problem is the loss of strength of treated cottons when chemical finishes are applied. Fabrics treated with 1,l,3-tris-(2,3-epoxypropoxy)butane by the process of this invention show a lower strength loss at a particular level of crease recovery than do other commercial polyepoxides.

While the polyepoxide finishes generally in use are not easily dispersed in a treating bath to give a homogeneous solution because of the presence of water insoluble polymers, 1,1,3-tris-(2,3-epoxypropoxy)butane, the novel compound employed in the process of this invention, has a distinct advantage of being miscible in all proportions with water at 25 C. so that solvents or emulsifying agents are not necessary in preparing the treating bath.

Thiis, it is only necessary to add the epoxy curing catalyst together with any desired conventionally used additives. While the above miscibility in water is an outstanding feature of 1,1,3-tris-(2,3-epoxypropoxy)butane, solutions of higher concentrations of the epoxide can be prepared by employing appropriate solvents or emulsifying agents such as dioxane, polyvinyl alcohol, and the like.

A further unique advantage of the polyepoxide used in the process of this invention is that while it possesses the ability to impart the desired wash-and-wear characteristics to textile fabrics it also has an additional feature in that it can be stripped from the fabric in the event it is desirable to return the cloth to its original condition, as for example, in a case of overtreatment of the fabric. The stripped fabric can subsequently be retreated with the same or a different polyepoxide to impart the desired wash-and-wear characteristics. This feature represents an advance over other polyepoxide textile finishes currently available to the industry.

In another aspect of the present invention, textile treating solutions can be prepared which contain mixtures of one or more polyepoxides and one or more known textile finishes, particularly the nitrogen-containing finishes, either alone or in the presence of an epoxy curing catalyst. The undesirable yellowing effect due to the chlorine retention properties of the nitrogenous textile resins, when such resins are used as the sole fin ish for white goods, is eliminated or greatly reduced when employed in conjunction with polyepoxides. Additionally, the combined finishes have a synergistic effect with enhanced wash-and-wear properties. Thus, excellent results are obtained, for example, by the use of 1,1,3-tris- (2,3-epoxypropoxy)butane in conjunction with dimethylol ethylene urea. Other aminoplasts are equally effective when used with polyepoxides and include, among others, for purposes of illustration, the melamine-formaldehyde resins, 1,3-dimethylol--ethyltetrahydro-S-triazin-2(lH)-one; monoand dimethylol ureas, methylated methylol ureas, and the like.

The textile treating solutions employed for imparting the wash-and-wear characteristics to the cellulosic or cellulosic-containing materials can also contain, in addition to the aforementioned polyepoxide, nitrogenous textile resins, plasticizers, natural resins, textile softening agents, stabilizers, and the like.

While the curing step can be accomplished by heating, it can be accelerated by the use of a suitable epoxy curing catalyst. A variety of catalysts are useful in the process of this invention with the borontrifiuoride complexes being preferred. Other acids, acidic salts, and Lewis acids are also suitable for this purpose. Examples of epoxy curing catalysts are the fiuoborates of magnesium, tin, cadmium and sodium as well as zinc; boron trifiuoride etherate, stannic chloride, boric acid, the alkane sulfonic acids, aluminum chloride, hydrochloric acid, phosphoric acid, oxalic acid, magnesium chloride, sodium sulfate, Zinc sulfate, aluminum sulfate, and the like. The amount of catalyst employed is not necessarily critical and can vary in amounts from about 0.01 percent to about 10 percent by weight of the treating solution, with a preferred range of from about 0.1 to about 5 percent.

The amount of polyepoxide to be applied to the textile material is an amount sufficient to give a desired washand-wear rating of 4 or 5 as hereinafter indicated. A preferred method is to immerse the fabric in an aqueous textile treating solution containing from about 1 to 30 percent by Weight of the polyepoxide, preferably 3 to 20 percent, and from 0.01 to 10 percent of the epoxy curing catalyst and then pass it through a squeeze roller. A second immersion and squeezing can be effected if necessary, leaving the fabric impregnated with approximately 60 to 120 percent of its own weight of solution. After this padding procedure, the fabric is mounted on a pin frame and dried at relatively low temperatures to remove water. While drying may be accomplished by allowing the fabric to remain in contact with the air, a temperature range of from about 35 C. to about C. is preferred. Since the drying time is not critical, a wider range of drying temperature can be employed equally as well.

Upon drying, the fabric is cured at a temperature sufficient to promote the reaction of the polyepoxide with the fibrous material being treated. In distinction to the great majority of polyepoxides which can be cured only at temperatures above 130 C., 1,l,3-tris-(2,3-epoxypropoxy)butane can be cured over an appreciably wider temperature range. Temperatures from about 200 C. to about C. can be employed for periods ranging from about 30 seconds to about 10 minutes, with the higher temperatures using the shorter curing period.

After the curing step, the fabric is scoured to remove unreacted polyepoxide or epoxy curing catalyst. Scouring is effected by washing in hot water (40 C. to 90 C.) containing a small quantity of detergent. The scouring conditions themselves are not critical as long as unreacted material is removed from the fabric. After scouring, the fabric is dried and evaluated.

The cellulosic textile fabrics used to illustrate the process of this invention were 80 x 80 cotton print cloth and 80 x 80 staple rayon fabric. The fabric was white, had been scoured and bleached, and was in suitable condition for application of resin treatment.

In the evaluation of the properties of the treated fabric, the following tests were conducted:

(a) Breaking strength; measured by the raveled strip method (American Society for Testing Materials D39- 49).

(b) Crease recovery; measured with the Monsanto tester (American Society for Testing Materials D1295- 53T). By this test the ability of a fabric to recover from a crushing fold is measured.

(0) Dimensional stability; American Association of Textile Chemists and Colorists, tentative test method 40-52.

(d) Wash-and-wear evaluation; by means of the following scale, the Wash-and-wear properties of the treated material were evaluated.

Scale: Evaluation As ironed. 4 Wearable. 3 Needs ironing. 2 Not acceptable.

1 Very wrinkled.

green and blue light. A simple yellowness index is provided by Yellowness A B where A, B and G represent the refiectances in amber, blue and green light, respectively. The index so obtained correlates closely with subjective evaluations. A white fabric has a yellowness which approaches zero, while an index in the range of 0.2 or 0.3 described a very yellow sample.

(7) Dry add-on; determined by measuring the increase in Weight of the fabric after treatment with the polyepoxide, and scouring to remove unreacted material; is a measurement of the total epoxide which has reacted with the fiber.

The following examples illustrate the present invention:

EXAMPLE I A treating solution was prepared which contained 15 percent by weight of 1,1,3-tris-(2,3-epoxypropoxy)butane and 0.5 percent by weight of zinc fluoborate, the remainder being water. A sample of 80 X 80 cotton print cloth was immersed in this solution, padded to a wet pick-up of 97 percent of the fabric weight and dried for 5 minutes at 40 C. The fabric was cured for 3 minutes at 120 C. and then laundered with an 0.1 percent solution of a built anionic detergent to remove residual reagents. The dry add-on after laundering was found to be 7.7 percent. The crease recovery of the treated sample was 74 percent, the warp breaking strength retained was 63 percent, and the sample had a wash-and-wear index of 3.

The original untreated fabric was immersed in water, dried and was found to have a crease recovery of only 44 percent.

EXAMPLE II A sample of 80 x 80 cotton print cloth was treated in a manner similar to that described in Example I, except that the concentration of zinc fluoborate catalyst was 1.0 percent by weight of the treating solution. The treated sample had a dry add-on of 10.4 percent, a crease recovery of 83 percent, a warp breaking strength retention of 59 percent, and wash-and-wear index of 4.

EXAMPLE III A sample of 80 x 80 cotton print cloth was treated in a manner similar to that described in Example I, except that the concentration of Zinc fluoborate catalyst was 2.0 percent by weight of the treating solution. The treated sample had a dry add-on of 12.6 percent, a crease recovery of 79 percent, a warp breaking strength retention of 54 percent, and a wash-and-wear index of 4.

EXAMPLE IV A sample of 80 x 80 cotton print cloth was treated in a manner similar to that described in Example I, except that the curing temperature employed was 200 C. The treated sample had a dry add-on of 9.1 percent, a crease recovery of 73 percent, a warp breaking strength retention of 50 percent, and a wash-and-wear index of 3.

EXAMPLE V A sample of x 80 cotton print cloth was treated in a manner similar to that described in Example IV, except that the concentration of zinc fluoborate catalyst was 1.0 percent by weight of the treating solution. The treated sample had a dry add-on of 11.1 percent, a crease recovery of 78 percent, a warp breaking strength retention of 61 percent and a wash-and-wear index of 4.

EXAMPLE VI EXAMPLE VII A treating solution was prepared which contained 14 percent by weight of 1,1,3-tris-(2,3-epoxypropoxy)butane and 1.44 percent by weight of zinc fluoborate, the remainder being water. A sample of 80 x 80 cotton print cloth was immersed in this solution, padded to a wet pickup of 77 percent of its weight and dried for 3 minutes at 70 C. The fabric was then cured for 3 minutes at C. and then laundered in an 0.1 percent solution of a built commercial anionic detergent to remove residual reagents. The dry add-on of the treated fabric was found to be 5.2 percent and the crease recovery 72 percent.

The treated fabric was found to be insoluble to a substantial degree after 24 hours of immersion in cuprammonium hydroxide solution, a solvent for cellulose. In contrast a sample of untreated cotton print cloth dissolved in the cuprammonium hydroxide solution in less than one hour.

EXAMPLE vnr A portion of the same fabric treated in Example VII was immersed in a solution of 0.1 N hydrochloric acid at 80 C. for a period of 30 minutes to remove the polyepoxide. After washing and drying the fabric, the dry add-on was found to be 1.9 percent. The sample was less soluble in cuprammoniurn hydroxide than the untreated cotton control, but appreciably more soluble than before hydrolysis.

EXAMPLE IX A treating solution was prepared which contained 15 percent by weight of 1,1,3-tris-(2,3-epoxypropoxy)butane and 0.5 percent by weight of zinc fluoborate, the remainder being water. A sample of 80 x 80 cotton print cloth was immersed in this solution, padded to a wet pick-up of 83 percent of the fabric weight and dried for 3 minutes at 75 C. The fabric was cured for 3 minutes at 200 C. and then laundered with a detergent to remove residual reactants. The dry add-on after laundering was found to be 8.0 percent. The crease recovery of the treated sample was 71 percent, the warp breaking strength retained was 7.5 percent by weight of 1,1,3-tris-(2,3-epoxypropoxy)- butane and 0.5 percent by weight of zinc fiuoborate, the remainder being water. The same sample of cloth from which the polyepoxide had been stripped was then immersed in this solution and padded to a wet pick-up of 72 percent and dried for 3- minutes at 75 C. The fabric was then cured for 3 minutes at 75 C. and 3 minutes at 140 C. The dry add-on after laundering was found to be 1.9 percent based on the weight of the treated sample after hydrolysis. The crease recovery was 61 percent and the breaking strength retained was 46 percent based on the strength of the untreated cotton print cloth.

EXAMPLE X Preparation of 1,1,3-Tris-(2,3-Epoxyprp0xy)Butane To 452 grams 1,1,3-trialloxybuta-ne (from the reaction of crotonaldehyde with allyl alcohol) which was heated with stirring to 50 C.55 0, there was added 1955 grams of a 27.2 percent solution of peracetic acid in ethyl acetate dropwise over a period of five hours. After an additional three hours the reaction was 91 percent complete as indicated by analysis for unreacted peracetic acid. The cooled reaction mixture was passed through a steam-heated stripper once at a pressure of 50 millimeters of mercury and again at 5 millimeters pressure to remove the volatiles from the product. The stripped product was then. flash-distilled to give an almost colorless liquid, which upon analysis gave 80 percent as 1,1,3-tris- (2,3-epoxypropoxy)butane by the pyridine hydrochloride method, in 63 percent yield based on peracetic acid. A sample of this product was redistilled through a short Vigreaux column to give colorless material, 87.5 percent as 1,1,3-tris-(2,3-epoxypropoxy)butane, boiling point 154 C. at a pressure of 0.6 millimeters. The material had a refractive index, n 30/ D, of 1.4593.

Although the invention has been illustrated by the preceding examples, the invention is not to be construed as limited to the materials employed in the above examples, but rather, the invention encompasses the generic area as hereinbeforc disclosed. Various modifications and embodiments of this invention can be made without departing from the spirit and scope thereof.

What is claimed is:

1. A process for treating cellulosic and cellulosic-containing textile material whereby said material is rendered both shrink and crease resistant while imparting to said material after laundering a soft smooth finish without ironing which comprises impregnating said textile material with a 1,1,3-tris-(2,3-epoxyalkoxy)butane and heating said impregnated textile material.

2. A process for treating cellulosic and cellulosic-containing textile material whereby said material is rendered both shrink and crease resistant while imparting to said material after laundering a soft smooth finish without ironing which comprises impregnating said textile material with 1,1,3-tris-(2,3-epoxypropoxy)butane and heating said impregnated textile material.

3. A process for treating cellulosic and cellulosiccontaining textile material whereby said material is rendered both shrink and crease resistant while imparting to said material after laundering a soft, smooth finish without ironing which comprises impregnating said textile material with an aqueous solution containing a mixture of 1,1,3-tris-(2,3-epoxypropoxy)butane and an epoxy curing catalyst; and drying and heating said impregnated textile material.

4. A process as claimed in claim 2 wherein the textile material is cotton.

5. A process as claimed in claim 2 wherein the textile material is rayon.

6. A process as claimed in claim 2 wherein the textile material is linen.

7. A process for treating cellulosic and cellulosiccontaining material whereby said material is rendered both shrink and crease resistant while imparting to said material after laundering a soft, smooth finish without ironing, which comprises impregnating said textile material with an aqueous solution containing a mixture of from about 1 to about 30 percent by weight of 1,1,3-tris- (2,3-epoxypropoxy)butane and from about 0.01 to about 10 percent by weight of an epoxy curing catalyst; and drying and heating said impregnated textile material.

8. A process as claimed in claim 7 wherein the epoxy curing catalyst is Zinc fluoborate.

9. A process for treating cellulosic and cellulosiccontaining textile material whereby said material is rendered both shrink and crease resistant while imparting to said material after laundering a soft, smooth finish Without ironing, which comprises impregnating said textile material with an aqueous solution containing a mixture of from about 3 to about 20 percent by weight of 1,1,3- tris-(2,3-epoxypropoxy)butane and from about 0.1 to about 5 percent by weight of zinc fluoborate; and drying and heating said impregnated material.

10. A process as claimed in claim 9 wherein the fabric is heated within the temperature range of from about 200 C. to about C. for a period of from about 30 seconds to about 10 minutes.

No references cited 

1. A PROCESS FOR TREATING CELLULOSIC AND CELLULOSIC-CONTAINING TEXTILE MATERIAL WHEREBY SAID MATERIAL IS RENDERED BOTH SHRINK AND CREASE RESISTANT WHILE IMPARTING TO SAID MATERIAL AFTER LAUNDERING A SOFT SMOOTH FINISH WITHOUT IRONING WHICH COMPRISES IMPREGNATING SAID TEXTILE MATERIAL WITH A 1,1,3-TRIS-(2,3-EPOXYALKOXY) BUTANE AND HEATING SAID IMPREGNATED TEXTILE MATERIAL. 